Novel bis-betaines and betaines within [1(4)]meta-heterophane frameworks

After prior selection of betaine building blocks for the construction of quadrupolar heterophane frameworks, a convergent "3+1" synthetic strategy is reported for the synthesis of the title macrocycles composed of heterocyclic betaine subunit(s). These typify the first example of simple cyclophanes constructed out of both highly pi-excessive and highly pi-deficient heteroaromatic moieties linked in a 1,3-alternating fashion. The chemical reactivity of the quadrupolar heterophanes 1a and 1c toward electrophiles under neutral conditions corroborated their bis-betaine structure. The structural features of the bis-betaines 1, betaines 2 x PF6 and 5 x X, and the corresponding dicationic [1(4)]heterophanes 3 x 2X and 4 x 2Cl were studied by 1H and 13C NMR spectroscopy and electrospray ionization mass spectrometry, and confirmed by single-crystal X-ray diffraction analysis of macrocycles 1a and 2a x PF6.     

Epoxy-silica/clay nanocomposite for silver-based antibacterial thin coatings: structure and ionic mobility

Journal of Solid State Electrochemistry - A novel material was developed using sol-gel chemistry and an environmental-friendly grafting process of clay nanoparticles. In a previous work of our...     

Total Syntheses of 11-Acetoxy-4-deoxyasbestinin D, 4-Deoxyasbestinin C,Asbestinin-10, -20, -21 and -23

Six members of the asbestinin family of marine diterpene natural products have been synthesized in an efficient and stereoselective manner from a single oxa-bridged intermediate. Five of these natural products have not been synthesized previously and the structures of four of them have been confirmed as those proposed originally or following revisions to the original structures. The fifth natural product—asbestinin-21—has been shown to be a diastereomer of the compound that had been proposed previously.     

New alkaloids from Phoebe grandis (Nees) Merr

The alkaloidal extract of the leaves of Phoebe grandis (nees) merr. have provided two new minor alkaloids; phoebegrandine D (1), a proaporphine-tryptamine dimer, and phoebegrandine E (2), an indoloquinolizidine. This is the first report on the occurrence of an indoloquinolizidine in the Phoebe species. The crude extract also exhibited antiplasmodial activity (IC50<8 microg mL-1). The structures of the novel compounds were elucidated by spectroscopic methods, notably 2D NMR and HRMS.     

Photoinduced electron transfer dynamics in porphyrin donor dyads

Intramolecular photoinduced electron transfer (PET) processes occurring in dyads with a free base porphyrin-tetraazaanthracene donor (P) and either a tetracyanonaphthoquinidodimethane (TCQ) or benzoquinone (BQ) acceptor linked by a rigid six σ-bond polynorbornane bridge ([6]) have been investigated. For P[6]BQ, PET in the polar solvent benzonitrile (_s = 25.9) occurs with a rate constant (k_PET) of 1.6 × 10⁸ s⁻¹ but is not evident in solvents less polar than tetrahydrofuran (_s = 7.52). For P[6]TCQ, highly efficient forward PET occurs in both polar and non-polar solvents (k_PET > 2 × 10¹⁰ s⁻¹). For P[6]TCQ the lifetime of the resulting charge-separated state decreases markedly with increasing solvent polarity. The results are discussed in the context of the likely mechanisms for electronic coupling and current theories for PET processes in such linked molecular systems.     

Effect of MWCNT content on thermal and shape memory properties of epoxy nanocomposites as material for morphing wing skin

Journal of Thermal Analysis and Calorimetry - In the present study, a shape memory epoxy polymer (SMEP) system was prepared from commercially available EPON 826 and NGDE, and then, 0.5%, 1.0% and...     

Free aluminium extraction from various reference materials and acid soils with relation to plant availability

The single extractions with 15 extractants (agents) (H₂O, KCl, NH₄Cl, NH₄F, CaCl₂, BaCl₂, CuCl₂, LaCl₃, Na₂S₂O₄, (NH₄)₂C₂O₄, Na₄P₂O₇, NTA, EDTA, DTPA, HCl), the optimised BCR (Community Bureau of Reference) three-step sequential extraction procedure (SEP) and the solid phase extraction (SPE) by the chelating ion-exchanger Iontosorb Salicyl (cellulose resin containing covalently bound salicylic acid functional groups) were used for the partitioning of Al in very acid soil samples taken from an area influenced by acid mine solutions. The precision, accuracy and repeatibility for all steps of the optimised BCR SEP were checked on the various reference materials (CRM 483 sewage sludge amended soil, CRM BCR 701 freshwater sediment, SRM 2710 and SRM 2711 Montana soils). Also the new indicative values of the optimised BCR SEP fractional Al concentrations were obtained for these reference materials. The aluminium amounts obtained by the used extraction procedures were valuated and discussed from the aspect of the Al concentration in the plants (grass) growing on the same studied soils. The aluminium toxicity indexes (ATI) calculated for the studied soils, the BaCl₂ and acetic acid soil extracts and the grass stems and roots were used for the assessment of the Al toxicity to the plants. The ATI value was defined as the ratio of the nutrient cations (Ca, Mg, K, Na) concentration sum to the Al concentration. The flame atomic absorption spectrometry (LOQ = 0.2 mg l⁻¹) and the inductively coupled plasma optical emission spectrometry (LOQ = 0.03 mg l⁻¹) were used for the aluminium quantification.     

Fullerene-templated synthesis of a cyclic porphyrin trimer using olefin metathesis

An olefination approach to the construction of covalently linked cyclic metalloporphyrin trimers is presented using fullerenes such as C(60) or C(70) as a template. Yields of the trimer approach 60%. In the absence of a template, the major product is the cyclic dimer (50% yield) with only a small amount of trimer (<10%) formed, indicating this is a template-directed approach.     

On-line two-dimensional liquid chromatography-tandem mass spectrometric determination of estrogens in sediments

The development of an on-line system for the simultaneous determination of α-estradiol, β-estradiol, estrone and 17α-ethynylestradiol in river sediments is described. The analytes were extracted from sediments by microwave-assisted extraction. A crude extract was directly analysed by a heart-cutting two dimensional high-performance liquid chromatography-ion trap-tandem mass spectrometry with an atmospheric pressure photoionization source operating in the positive mode. The method shows excellent performance in terms of accuracy, precision, and sensitivity. The accuracy of each estrogen was in the range of 98.8-107.1%. Intra-batch and inter-batch precisions were in the range of 6.2-7.0% and 8.3-9.5%, respectively. The limits of detection ranged from 90 to 250 pg g(-1). A significant reduction in the total analysis time and a reduction in sample manipulation are the main advantages of the proposed method. Finally, the method was applied on real sediment samples.